JPH0830028B2 - Fluorine-containing alicyclic compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fluorine-containing alicyclic compound and a method for producing the same.

(Prior Art) Conventionally, as a fluorine-containing epoxy compound, for example, USP 4,0
No. 45,408 discloses compounds having the following structural formula.

These compounds can be cured by irradiation with active energy rays such as heat, light, and electron beams in the presence of a curing agent and / or a catalyst, and are used as raw materials for adhesives, and cured products are optical. It is useful as a material. However, these compounds are unsatisfactory in water resistance, have a high refractive index and are insufficient in terms of compatibility with optical glass.

(Problems to be Solved by the Invention) An object of the present invention is to provide a fluorine-containing alicyclic compound having excellent water resistance, refractive index, heat resistance, strength and the like, and a method for producing the same.

(Means for Solving Problems) The present invention provides a general formula (M is the formula A divalent organic group consisting of at least one cycloaliphatic hydrocarbon group which may have a substituent,
R represents an alkyl group having 1 to 5 carbon atoms, OH, CH ₃ , NH ₂ , halogen, or a fluoroalkyl group having 1 to 20 carbon atoms, l ₁ , l ₂
And l ₃ are each 0 or an integer of 1 to 10 and represent the number of substituents R, and when the integer is 2 or more, R may be the same or different, and even when the integer is 1. When R is 2 or more in one organic group, R may be the same or different and is an organic group composed of 2 or more of the above-mentioned cycloaliphatic hydrocarbon groups which may have a substituent. In this case, they may be linked by O, S, CH ₂ or may form a condensed ring. X is And Y is H or CH ₃ , and n is 0 or a positive number from 0 to 30. ) Related to a fluorine-containing alicyclic compound represented by

In the general formula (1) of the present invention, a preferable representative example of the divalent organic group represented by M and consisting of the cycloaliphatic hydrocarbon group is, for example, And a divalent group represented by Here, R represents a substituent, and l ₁ , l ₂ and l ₃ are 0 or 1 to 1 respectively.
An integer of 10 indicates the number of substituents R, and when the integer is 2 or more, the Rs may be the same or different, and even when the integer is 1, R is 2 or more in one organic group. In some cases, R may or may not be the same. As the substituent, for example, an alkyl group having 1 to 5 carbon atoms, OH, CH ₃ , NH ₂ ,
Examples thereof include halogen (F, Cl, Br, etc.) and fluoroalkyl groups having 1 to 20 carbon atoms.

X is a glycidyl group (Gly group) or a group obtained by reacting this with acrylic acid or methacrylic acid, and n
Is 0 or a positive number, and particularly preferably a number in the range of 0-30.

The fluorine-containing compound of the present invention has, for example, the general formula The compound represented by (M is the same as above) is reacted with (a) epichlorohydrin and a dehydrochlorinating agent, or (b) after reacting epichlorohydrin and a dehydrochlorinating agent, further reacted with acrylic acid or methacrylic acid. It is obtained by

A solvent is not always necessary for the reaction, but methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and the like can also be used. ECH for compound (2)
Is preferably used in a molar amount of about 2 to 100 times. Also NaOH, K
Compound (2) with dehydrochlorination agents such as OH, LiOH, and Ca (OH) ₂
It is preferred to use about 1-20 equivalents to the OH equivalents of. A catalyst is not always necessary, but a quaternary ammonium salt such as trimethylbenzylammonium chloride or tetramethylammonium bromide can be used in a proportion of about 0.01 to 10% by weight based on the reaction system. The reaction temperature can be appropriately selected, but is preferably in the range of about 50 to 200 ° C.

Next, in the reaction of the above-obtained diglycidyl ethers with acrylic acid or methacrylic acid, a solvent is not always necessary, but benzene, toluene, xylene, MEK, MIBK and the like can be used. About 1 to about 1 equivalent of epoxy group of diglycidyl ether
It is preferable to use 50 mol. Quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium bromide or trimethylamine,
A tertiary amine such as triethylamine is used as a catalyst in an amount of about 0.01 to 10% by weight based on the reaction system. It is preferable to add hydroquinone, hydroquinone monoethyl ether, catechol, t-butylcatechol, phenothiazine or the like as a thermal polymerization inhibitor at a ratio of about 0.001 to 10% by weight based on the reaction system. The reaction temperature can be appropriately selected about 50
A range of up to 200 ° C is preferred.

The target fluorine-containing compound of the present invention represented by the general formula (1) can be separated and purified by a conventional method such as extraction, concentration, distillation, recrystallization and the like.

Among the fluorine-containing compounds of the present invention, an epoxy compound in which X is a Gly group is, for example, ((a) a curing agent used in epoxy resins such as polyamines, polyols and acid anhydrides, (b) imidazoles, Mixing with a thermosetting catalyst used for epoxy resin such as Lewis acid (BF ₃ complex), (c) a photocuring catalyst used for epoxy resin such as diazonium salt, sulfonium salt, phosphonium salt, etc., It can be used as an adhesive or the like.

Among the fluorine-containing compounds of the present invention, the compounds to which acrylic acid or methacrylic acid is added are, for example, the thermal polymerization initiation of azo compounds (azobisisobutyronitrile etc.) or peroxides (benzoyl peroxide etc.) A known compound as an agent can be added to form an adhesive. Further, a photopolymerization initiator (benzophenone, etc.) or the like may be added to form an adhesive. In this case, vinyl compounds (methyl acrylate, acrylic acid-2-
It can also be used as an adhesive or the like by adding the above-mentioned initiator to the mixture.

(Effect of the invention) The fluorine-containing compound of the present invention is excellent in water resistance, refractive index, strength, etc., and in the presence of various curing agents, curing catalysts, initiators, active energy such as heat, light, and electron beams. It can be cured by irradiation with rays, and by using it in this way, an excellent adhesive can be provided, and the cured product is useful as an optical material.

(Example) Below, a reference example and an example are given and demonstrated.

Reference Example 1 [Synthesis of bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) benzene] 117 g (1.5 mol) of benzene and 31 g of anhydrous aluminum chloride
(0.23 mol) in a flask equipped with a stirrer,
While stirring, 500 g (3 mol) of hexafluoroacetone was introduced at a rate of about 5 g / min at room temperature. The reaction mixture was distilled under reduced pressure to give bis (1,1,1,2) in which the molar ratio of m-form to p-form was 85:15.
1,3,3,3-hexafluoro-2-hydroxyisopropyl) benzene (102-106 ℃ / 20mmHg) 517g (1.26mol)
I got The yield based on hexafluoroacetone is
It was 84%.

Reference Example 2 300 g of bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) benzene prepared in Reference Example 1 (0.
(73 mol) and 300 ml of isopropanol were placed in a Hastelloy autoclave, and 30 g of carbon powder supporting the catalyst rhodium (rhodium content, 5% by weight relative to the total amount) was added, and the mixture was stirred at 155 ° C. After heating to
It was pressurized to 60 kg / cm ² G with hydrogen and reacted for 4.5 hours.

After cooling to room temperature, the carbon powder supporting the catalyst was separated, isopropanol was distilled off, and the residue was distilled under reduced pressure.
287 g (0.69 mol) of bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexane (96 to 100 ° C / 6 mmHg), which is a fluorine-containing alicyclic diol, was obtained.
The yield was 94%. ¹ H-NMR (δppm in CCl ₄ ) 3.1 (2H, s, OH), 1.1 to 2.5 (10H, br, -CH-, -CH _2- ) Example 1 Bis (1 obtained in Reference Example 2 , 1,1,3,3,3-Hexafluoro-2-hydroxyisopropyl) cyclohexane (Compound A) 86 g (0.21 mol) and epichlorohydrin 382
g (4.13 mol) are mixed and sodium hydroxide 16.9 g (0.42 mol
Mol) and 2 ml of water were added, and the mixture was heated to reflux with stirring. After reacting for 10 hours, excess sodium chloride was removed with a glass filter, and excess epichlorohydrin was distilled off under reduced pressure. When the residue was examined by gel permeation chromatography (GPC), the compound of n = 0,1,2 in the general formula (1) was contained at a ratio of 93: 6: 1 (area ratio on the chromatogram). It was GPC conditions are columns Shodex KF
-801, KF-802, 30 cm each, the solvent is chloroform. The residue is distilled to obtain the general formula (1) as a fraction of 138-150 ℃ / 1mmHg.
Diglycidyl ether of compound A in which n = 0 in
Obtained 50 g. ¹ H-NMR (in CDCl ₃ , TMS standard, δppm) 1.4,2.0 br 10H Cyclohexane ring -CH-, -CH ₂ -2.7 m 4H 3.1 m 2H 3.7 m 4H Example 2 Compound A obtained according to the method described in Reference Example 2 was treated at 10 ° C.
When left for 1 week, crystals were precipitated. Pass this, wash with trichlorotrifluoroethane and wash with 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexane (Compound B) 26 g (0.063 mol) Got 117 g of epichlorohydrin (1.
26 mol) were mixed, 5.1 g (0.13 mol) of sodium hydroxide and 0.6 ml of water were added, and the mixture was refluxed under stirring for 10 hours. The produced sodium chloride was separated, the excess epichlorohydrin was distilled off, and the residue was distilled to obtain 16 g of diglycidyl ether of compound B as a fraction at 147 to 151 ° C / 1 mmHg. ¹ H-NMR (in CDCl ₃ , TMS standard, δppm) 1.4,2.0 br 10H Cyclohexane ring -CH-, -CH ₂ -2.7 m 4H 3.1 m 2H 3.7 m 4H Example 3 57 g (0.108 mol) of diglycidyl ether of Compound A synthesized according to the method described in Example 1 and 18.0 acrylic acid
g (0.25 mol) was added to 100 ml of toluene, 1 g of trimethylbenzylammonium chloride and 0.1 g of p-methoxyphenol were added, and the mixture was heated to reflux with stirring. After 14 hours, heating was stopped and the mixture was cooled to room temperature. The reaction solution was washed with saturated saline until the aqueous layer showed no acidity, dried over anhydrous sodium sulfate, 0.1 g of p-methoxyphenol was added, and 80-9 under a pressure of 1-2 mmHg.
The solvent is removed by heating at 0 ° C., and as a viscous liquid, n = 0 and X in the general formula (1) To obtain Compound C (63 g).

IR (liquid film, cm ¹ ) 3400 OH, 2900 CH, CH ₂ , 1722 C = O, 1635 C = C, 1402 C = C Example 4 Methacrylic acid 2 in place of acrylic acid in Example 3
The same operation as in Example 3 was carried out except that 1.5 g was used, and n = 0 and X in the general formula (1) were A compound D (64 g) was obtained.

IR (liquid film, cm ¹ ) 3400 OH, 2900 CH, CH ₂ , 1725 C = O, 1640 C = C, 1404 C = C Test Example 1 Refractive indices of the compounds of Examples 1 and 2 and the compound of Comparative Example 1 below. The results of measuring (n _D ²³ ) are shown in Table 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08G 59/30 NHR 65/28 NQP 65/48 NQH // C09J 163/00 JFM (72) Inventor Kozaburo Nakamura 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corp. (72) Inventor Toru Maruno 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corp. (56) Reference Document JP-A-62-89719 (JP, A) US Patent 3706772 (US, A) US Patent 3879430 (US, A) Amer. Chem. Soci. , Vol. 31, No. 1 (1971), p. 546−551

Claims (2)

[Claims] 1. A general formula (M is the formula R is a divalent organic group consisting of at least one cyclic aliphatic hydrocarbon group which may have a substituent,
Represents an alkyl group having 1 to 5 carbon atoms, OH, CH ₃ , NH ₂ , halogen, or a fluoroalkyl group having 1 to 20 carbon atoms, l ₁ , l ₂
And l ₃ are each 0 or an integer of 1 to 10 and represent the number of substituents R, and when the integer is 2 or more, R may be the same or different, and even when the integer is 1. When R is 2 or more in one organic group, R may be the same or different and is an organic group composed of 2 or more cyclic aliphatic hydrocarbon groups which may have the above-mentioned substituents. In this case, they may be linked by O, S, CH ₂ or may form a condensed ring. X is And Y is H or CH ₃ , and n is 0 or a positive number from 0 to 30. ) A fluorine-containing alicyclic compound represented by 2. General formula (M is the formula R is a divalent organic group consisting of at least one cyclic aliphatic hydrocarbon group which may have a substituent,
Represents an alkyl group having 1 to 5 carbon atoms, OH, CH ₃ , NH ₂ , halogen, or a fluoroalkyl group having 1 to 20 carbon atoms, l ₁ , l ₂
And l ₃ are each 0 or an integer of 1 to 10 and represent the number of substituents R, and when the integer is 2 or more, R may be the same or different, and even when the integer is 1. When R is 2 or more in one organic group, R may be the same or different and is an organic group composed of 2 or more of the above-mentioned cycloaliphatic hydrocarbon groups which may have a substituent. In this case, they may be linked by O, S, CH ₂ or may form a condensed ring. ) Is reacted with epichlorohydrin and a dehydrochlorination agent, or (b)
A general formula characterized by reacting epichlorohydrin with a dehydrochlorinating agent and then further reacting with acrylic acid or methacrylic acid. (M is the same as above. X is Or And Y is H or CH ₃ , and n is 0 or a positive number from 0 to 30. ) A method for producing a fluorine-containing alicyclic compound represented by: